Functional end-group polymers derived from free-radical chain transfer. I. Kinetic prediction of functionality

The kinetic scheme describing chain transfer in free-radical polymerizations, the Mayo equation, has been rearranged to yield the probability of generating a functional end group by chain transfer (e.g., to a disulfide). The prediction is that a mixture of functional and nonfunctional ends occurs. Examination of literature data shows a number of systems produce more functionality than predicted. Hence, the challenge to devise a new kinetic scheme to account for the increased functionality is made (e.g., by selective reaction of initiator with chain-transfer agent).